COATING FOR A CoCrMo SUBSTRATE

ABSTRACT

A coating for a CoCrMo substrate including a first layer located directly on the substrate and including Ta(CoCrMo) 0.5-2.0 , a second layer located directly on the first layer and including tantalum, a third layer located directly on the second layer and including tantalum carbide, and a fourth layer located directly on the third layer and including diamond-like carbon (DLC).

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation in part of U.S. patent applicationSer. No. 13/087,013, filed Apr. 14, 2011, now pending, which in turnclaims the benefit of U.S. Provisional Patent Application No.61/324,664, filed Apr. 15, 2010, all of which are incorporated herein byreference in their entirety.

FIELD OF THE INVENTION

The present invention generally relates to coatings on CoCrMosubstrates, for example, Co28Cr6Mo substrates. More particularly thepresent invention relates to diamond-like carbon (DLC) coatings havingexcellent biostability. Some embodiments of the invention relate to asubstrate with a DLC coating. Further embodiments of the inventionrelate to methods for applying a DLC coating to a substrate.

BACKGROUND OF THE INVENTION

The use of diamond-like carbon (DLC) coatings is known in the medicalindustry as a means to decrease the frictional wear of metalliccomponents. DLC coatings have been used, for example, on articulatingcomponents of medical devices, e.g., hip replacements, to reduce surfacewear. In these devices, the DLC-coated component typically articulatesagainst a polymeric or DLC-coated counterpart. For example, a total discreplacement device for the spine may have a DLC-coated titanium alloycomponent that articulates against a polyethylene counterpart.

DLC coatings applied directly on to a substrate may, however,demonstrate poor adhesion stability. Due to the deposition mechanism,DLC coatings can possess excessive compressive stress in the GPa range,which favors delamination of the DLC coating from a substrate. Forexample, published data on certain currently available DLC-coated hipjoints exhibit massive failures after 9 years in vivo.

FIG. 6 shows the revision rates of certain DLC-coated hip joint implantsaccording to the prior art gained from a 101 implants study by Taeger etal. (Materialwissenschaften und Werkstofftechnik 2003; 34(12):1094-1100, incorporated herein by reference in its entirety). FIG. 7shows a hip joint head explant from the Taeger series. As can be seen,the DLC-coating has failed and caused significant wear. The origin ofthe failures is small delaminated spots on the DLC surface, whicheventually combined to give one massive failure. Upon closer inspection,the failures appear roughly circular and can be shown to originate froma small point of failure, probably a pinhole as shown in FIG. 8.Delamination occurred in a circular fashion from an initial spot in thecenter.

FIG. 9 shows the delamination of the Taeger coating system originatingfrom an artificial defect. The delamination speed rapidly increasesafter 240 days, at which time the storage medium was exchanged fromphosphate buffered saline (PBS) to calf serum. The other data pointsgive the energy sustained by and stored in the coating system.

Thus, there remains a need for an improved DLC coating with improvedlong-term adhesion in vivo.

SUMMARY OF THE INVENTION

The present invention, in some embodiments, includes a CoCrMo substratehaving a coating. In some embodiments, the coated CoCrMo substrate canbe used in a medical device, for example, a joint prosthesis.

In one embodiment of the present invention, a coating for a CoCrMosubstrate includes four layers. In one embodiment, the four layersinclude a first layer including Ta(CoCrMo)_(0.5-2.0), a second layerincluding tantalum, a third layer including tantalum carbide, and afourth layer including diamond-like carbon (DLC). In one embodiment, thecoating includes only said four layers. In one embodiment, the firstlayer consists essentially of Ta(CoCrMo)_(0.5-2.0). In one embodiment,the second layer consists essentially of tantalum. In one embodiment,the third layer consists essentially of tantalum carbide. In oneembodiment, the fourth layer consists essentially of diamond like carbon(DLC).

In some embodiments, the first layer is disposed directly on thesubstrate. In some embodiments, the first layer has a thickness fromabout 1 nm to about 5 nm, preferably from about 2 nm to about 4 nm. Thefirst layer, according to some embodiments, has an oxygen content lessthan atomic %, preferably less than 3 atomic %.

In some embodiments, the second layer is disposed directly on the firstlayer. In some embodiments, the second layer includes alpha-tantalum. Insome embodiments, the second layer is essentially free of beta-tantalum.In some embodiments, the second layer is doped with tungsten, niobiumand/or titanium, for example, at about 0.1 atomic % to about 10 atomic%. In further embodiments, the second layer has a minimum thickness of20 nm, preferably a minimum thickness of 50 nm. In yet furtherembodiments, the second layer has a maximum thickness of 1000 nm,preferably a maximum thickness of 200 nm. The second layer, according tosome embodiments, has an oxygen content less than 5 atomic %, preferablyless than 3 atomic %.

In some embodiments, the third layer is disposed directly of the secondlayer. In some embodiments, the third layer has a minimum thickness of0.5 nm, preferably a minimum thickness of 4 nm. In further embodiments,the third layer has a maximum thickness of 10 nm, preferably of amaximum thickness of 6 nm. The third layer, according to someembodiments, has an oxygen content less than 5 atomic %, preferably lessthan 3 atomic %.

In some embodiments, the fourth layer is disposed directly on the thirdlayer. In some embodiments, the fourth layer has a minimum thickness of200 nm, preferably a minimum thickness of 500 nm. In some embodiments,the fourth layer has a maximum thickness of 10 μm, preferably of amaximum thickness of 5 μm. The fourth layer, according to someembodiments, has a hydrogen content of at least 1 atomic %. In furtherembodiments, the fourth layer has a hydrogen content of less than 35atomic %, preferably of less than 23 atomic %.

A coating according to some embodiments of the present invention, has amean roughness R_(a) below 50 nm. In further embodiments, the coatinghas a maximum roughness R_(t) below 200 nm. In some embodiments, thecoating has a total thickness in the range of about 0.5 μm to about 10μm.

In other embodiments, the coating is penetrated by a hole reaching thesubstrate. In one variation of this embodiment, the hole has a diameterd≦10.

A method for applying a coating to a CoCrMo substrate, according to someembodiments of the present invention, includes depositing anadhesion-promoting interlayer onto the substrate and depositing a DLClayer onto the adhesion-promoting interlayer. In some embodiments, amethod for coating a CoCrMo substrate includes: a) inserting the CoCrMosubstrate into a vacuum system; b) cleaning the CoCrMo substrate by Ar⁺ion bombardment; c) depositing a Ta adhesion-promoting interlayer ontothe CoCrMo substrate; and d) initiating DLC growth on the Taadhesion-promoting interlayer. In some embodiments, the Taadhesion-promoting interlayer is deposited onto the CoCrMo substrate bysputtering, for example, at a thickness of about 10 nm to about 1 μm.

BRIEF DESCRIPTION OF THE DRAWINGS

Several embodiments of the invention will be described in the followingby way of example and with reference to the accompanying drawings inwhich:

FIG. 1 shows an uncoated (left) and a coated (right) CoCrMo spinal diskimplant according to one embodiment of the invention mounted on testingsockets;

FIG. 2 shows the accumulated wear volume of the uncoated and coatedspinal disks of FIG. 1 run in a spine simulator;

FIG. 3A shows a focused ion beam cross-cut applied at the edge of adefect found on a DLC-coated implant using the interlayer system of anembodiment of the present invention;

FIG. 3B shows a magnification of a crack stopped and contained at theinterlayer system of FIG. 3A;

FIG. 4 shows a tantalum-based interlayer system according to anotherembodiment with an oxygen content of 3.5 atomic %;

FIG. 5 shows XRD scans of Ta layers featuring different oxygencontaminations as grown in accordance with embodiments of the presentinvention;

FIG. 6 shows the revision rates of DLC-coated hip joint implantsaccording to the prior art;

FIG. 7 shows a hip joint head explant according to the prior art with afailed DLC-coating causing significant wear;

FIG. 8 shows the delamination on an implant DLC layer according to theprior art (SEM image); and

FIG. 9 shows the delamination of a coating system according to the priorart originating from an artificial defect.

DETAILED DESCRIPTION

The present invention, according to some embodiments, includes coatingsfor a substrate which may be used, for example, in medical devices. Inother embodiments, the present invention includes a substrate having acoating as described herein. In some embodiments, the substrate is acomponent of a medical implant, for example, a joint prosthesis, a hipreplacement, a spinal disc prosthesis, a bone plate, and the like. Insome embodiments, the substrate is a component of a device subject towear.

In some embodiments, the substrate is a metallic substrate. In someembodiments, the substrate includes a metal alloy. In preferredembodiments of the invention, the substrate is acobalt-chromium-molybdenum (CoCrMo) substrate, for example, a Co28Cr6Mosubstrate.

A coating in accordance with some embodiments of the present inventionincludes a plurality of layers. In some embodiments, each of theplurality of layers includes a different chemical composition. In someembodiments, the coating includes at least a first layer and a secondlayer. In some embodiments, the coating includes at least a first layer,a second layer, and a third layer. In some embodiments, the coatingincludes at least a first layer, a second layer, a third layer, and afourth layer. In some embodiments, the coating includes no more thanfour layers. In some embodiments, the coating consists of four layers.

In some embodiments, a multi-layer coating according to presentinvention includes blending between adjacent layers. In someembodiments, a first layer of a coating of the present inventionincludes a blended interface with a second layer of the coating, in someembodiments, a second layer of a coating of the present inventionincludes a blended interface with a third layer of the coating. In someembodiments, a third layer of a coating of the present inventionincludes a blended interface with a fourth layer of the coating. In someembodiments, the blended interfaces of a multi-layer coating are eachabout 1 nm in thickness or less.

In some embodiments, at least one of the plurality of layers includestantalum (Ta), a Ta alloy, or a Ta compound. In some embodiments, thecoating includes three different layers wherein each of the layersincludes Ta, a Ta alloy, or a Ta compound. In some embodiments, at leastone of the plurality of layers, preferably the outer-most layer (i.e.,the layer furthest away from the substrate), includes diamond-likecarbon (DLC). In some embodiments, at least one of the plurality oflayers consists essentially of DLC. In some embodiments, at least one ofthe Ta-containing layers serves as an adhesion-promoting interlayer toaid in chemically attaching the DLC layer to the substrate via alloying.In some embodiments, all of the Ta-containing layers serves as anadhesion-promoting interlayer.

In some embodiments, a coating in accordance with the present inventionincludes a first layer disposed directly on a substrate, e.g., a CoCrMosubstrate. In some embodiments, the first layer is composed of amaterial different than the substrate. In some embodiments, the firstlayer includes a CoCrMo alloy. In some embodiments, the first layerconsists essentially of a CoCrMo alloy. In some embodiments, the firstlayer includes tantalum (Ta). In some embodiments, the first layerconsists essentially of tantalum. In some embodiments, the first layerincludes a tantalum alloy. In some embodiments, the first layer consistsessentially of a tantalum alloy. In some embodiments, the first layerincludes Ta(CoCrMo), e.g., Ta(CoCrMo)_(0.5-2.0). In some embodiments,the first layer consists essentially of Ta(CoCrMo), e.g.,Ta(CoCrMo)_(0.5-2.0). In some embodiments, the first layer has an oxygencontent less than 5 atomic %, preferably less than 3 atomic %. In someembodiments, the first layer has an oxygen content less than 2 atomic %.In some embodiments, the first layer has an oxygen content less than 1atomic %. In some embodiments, the first layer has an oxygen contentless than 0.5 atomic %. In some embodiments, high oxygen content (e.g.,greater than 5 atomic %) may weaken the interface of the first layer andenable various failure mechanisms (e.g., cracking). When present at highlevels (e.g., greater than 5 atomic %), oxygen in some embodiments mayterminate potential interatomic bonds and induce phase changes that maymake the coating brittle and susceptible to corrosive attack.

In some embodiments, the first layer has a thickness of at least 1 nm.In some embodiments, the first layer has a thickness of at least 2 nm.In some embodiments, the first layer has a thickness of at least 3 mm.In some embodiments, the first layer has a thickness of at least 4 nm.In some embodiments, the first layer has a thickness of at least 5 nm.In some embodiments, the first layer has a thickness of about 1 nm toabout 5 nm, preferably about 2 nm to about 4 nm. In some embodiments,the first layer has a thickness of 1 nm to 5 nm, preferably 2 nm to 4nm. In some embodiments, the first layer has a thickness of no more than5 nm. In some embodiments, the first layer has a thickness of no morethan 4 nm.

In some embodiments, a coating according to the present inventionfurther includes a second layer disposed directly on the first layer,such that the first layer is positioned between the substrate and thesecond layer with no intervening layer. In some embodiments, there isblending between the first layer and the second layer at theirinterface. In some embodiments, the blended interface is no more than 1nm in thickness, in some embodiments, the second layer is composed of amaterial different than the substrate and the first layer.

In some embodiments, the second layer includes tantalum. In someembodiments, the second layer consists essentially of tantalum. In someembodiments, the second layer includes alpha-tantalum. In someembodiments, the second layer consists essentially of alpha-tantalum.Alpha-tantalum has been found to be, according to some embodiments, amacroseopically ductile phase whereas other tantalum phases (e.g.,beta-tantalum) may be relatively brittle. By excluding relativelybrittle beta-tantalum from the coating, a more ductile coating may beobtained in some embodiments. In some embodiments, a more ductilecoating provides better long-term adhesion of the coating to thesubstrate. Therefore, in preferred embodiments, the second layer issubstantially free of beta-tantalum. In some embodiments, the secondlayer includes amorphous alpha tantalum and nanocrystalline alphatantalum. In some embodiments, the second layer consists essentially ofamorphous alpha tantalum and nanocrystalline alpha tantalum. Moreover,in some embodiments, the second layer has an oxygen content less than 5atomic %, preferably less than 3 atomic %. Higher oxygen content (e.g.,greater than 5 atomic %), in some embodiments, may lead to beta phasetantalum formation, which can be macroscopically brittle. Accordingly inpreferred embodiments it is desirable to keep the oxygen level, duringdeposition sufficiently low so that the resulting coating layer has, forexample, an oxygen content less than 5 atomic %, preferably less than 3atomic %. In some embodiments, the second layer has an oxygen contentless than 2 atomic %. In some embodiments, the second layer has anoxygen content less than 1 atomic %. In some embodiments, the secondlayer has an oxygen content less than 0.5 atomic %. When present at highlevels (e.g., greater than 5 atomic %), oxygen in some embodiments mayterminate potential interatomic bonds and induce phase changes that maymake the coating brittle and susceptible to corrosive attack.

In further embodiments, the tantalum is deposited withalpha-phase-stabilizing dopands. In some embodiments, the second layerincludes Ta (e.g., alpha-tantalum) doped with niobium (Nb) tungsten (W),and/or titanium (Ti). In some embodiments, the second layer consistsessentially of Ta (e.g., alpha-tantalum) doped with niobium (Nb),tungsten (W), and/or titanium (Ti). Nb, W, and/or Ti in some of theseembodiments may be present in the second layer at about 0.1 atomic % toabout 10 atomic %. Doping with alpha-phase-stabilizing dopands such asNb, W, and/or Ti, according to some embodiments, leads to astabilization of the alpha-phase composition and an increase of theoxygen tolerance, i.e., the level of oxygen contamination that wouldstill allow for long-term adhesion of the coating to the substrate. Insome embodiments, a layer including tantalum doped withalpha-phase-stabilizing dopands may have an oxygen tolerance that allowsfor an oxygen content greater than 3 atomic %. In some embodiments, alayer including tantalum doped with alpha-phase-stabilizing dopands mayhave an oxygen tolerance that allows for an oxygen content greater than5 atomic %.

In some embodiments, the second layer has a thickness of at least 20 nm.In some embodiments, the second layer has a thickness of at least 30 nm.In some embodiments, the second layer has a thickness of at least 40 nm.In some embodiments, the second layer has a thickness of at least 50 nm.In some embodiments, the second layer has a thickness of at least 100nm. In some embodiments, the second layer has a thickness of about 20 nmto about 1000 mm, preferably about 50 nm to about 200 nm. In someembodiments, the second layer has a thickness of 20 nm to 1000 nm,preferably 50 nm to 200 nm. In some embodiments, the second layer has athickness of no more than 1000 nm. In some embodiments, the second layerhas a thickness of no more than 500 nm. In some embodiments, the secondlayer has a thickness of no more than 200 nm.

In some embodiments, a coating according to the present inventionfurther includes a third layer disposed directly on the second layer,such that the first layer is positioned between the substrate and thesecond layer, and the second layer is positioned between the first layerand the third layer. In some embodiments, the third layer is composed ofa material different than the substrate, the first layer, and the secondlayer. In some embodiments, there is no intervening layer between thesecond layer and the third layer. In some embodiments, there is blendingbetween the second layer and the third layer at their interface.

In some embodiments, a third layer includes tantalum. In someembodiments, a third layer consists essentially of tantalum. In someembodiments, the third layer includes a tantalum compound. In someembodiments, the third layer consists essentially of a tantalumcompound. In some embodiments, the third layer includes or consistsessentially of a carbide. In some embodiments, the third layer consistsessentially of a carbide. In some embodiments, the third layer includestantalum carbide. In some embodiments, the third layer consistsessentially of tantalum carbide. In some embodiments, the third layerhas ma oxygen, content less than 5 atomic %, preferably less than 3atomic %. In some embodiments, the third layer has an oxygen contentless than 2 atomic %. In some embodiments, the third layer has an oxygencontent less than atomic %. In some embodiments, the third layer has anoxygen content less than 0.5 atomic %. When present at high levels(e.g., greater than 5 atomic %), oxygen in some embodiments mayterminate potential interatomic bonds and induce phase changes that maymake the coating brittle and susceptible to corrosive attack.

In some embodiments, the third layer has a thickness of at least 0.5 nm.In some embodiments, the third layer has a thickness of at least 1 nm.In some embodiments, the third layer has a thickness of at least 2 nm.In some embodiments, the third layer has a thickness of at least 3 nm.In some embodiments, the third layer has a thickness of at least 4 nm.In some embodiments, the third layer has a thickness of about 0.5 nm toabout 10 nm, preferably about 4 nm to about 6 nm. In some embodiments,the third layer has a thickness of 0.5 nm to 10 nm, preferably 4 nm to 6mm. In some embodiments, the third layer has a thickness of no more than10 nm. In some embodiments, the second layer has a thickness of no morethan 6 nm.

In some embodiments, a coating according to the present inventionfurther includes a fourth layer disposed directly on the third layer,such that the first layer is positioned between the substrate and thesecond layer, the second layer is positioned between the first layer andthe third, and the third layer is positioned between the second layerand the fourth layer. In some embodiments, the fourth layer is composedof a material different than the substrate, the first layer, the secondlayer, and the third layer. In some embodiments, there is no interveninglayer between the third layer and the fourth layer. In some embodiments,there is blending between the third layer and the fourth layer at theirinterface.

In some embodiments, the fourth layer includes diamond-like carbon(DLC). In some embodiments, the fourth layer consists essentially ofdiamond-like carbon (DLC). In some embodiments, the fourth layer has ahardness of about 10 GPa to about 80 GPa as measured by nanoindentation.In some embodiments, the fourth, layer has a hardness greater than 10GPa as measured by nanoindentation. In some embodiments, the fourthlayer has a hardness greater than 20 GPa as measured by nanoindentation.In some embodiments, the fourth layer has a hardness greater than 30 GPaas measured by nanoindentation. In some embodiments, the fourth layerhas a hardness greater than 40 GPa as measured by nanoindentation. Insome embodiments, the fourth layer has a hardness greater than 50 GPa asmeasured by nanoindentation. In some embodiments, the fourth layer has ahardness greater than 60 GPa as measured by nanoindentation, in someembodiments, the fourth layer has a hardness greater than 70 GPa asmeasured by nanoindentation. In some embodiments, the fourth layer has ahardness greater than 80 GPa as measured by nanoindentation.

In some embodiments, a high hydrogen content (e.g., greater than 35atomic %) may result in reduced hardness of the fourth layer due toincreased hydrogen bonding. Accordingly, in preferred embodiments, thefourth layer has a hydrogen content of no more than 35 atomic %. In someembodiments, the fourth layer has a hydrogen content of less than 35atomic %, preferably less than 23 atomic %. In some embodiments, thefourth layer has a hydrogen content of less than 15 atomic %. In someembodiments, the fourth layer has a hydrogen content of at least 1atomic %.

In some embodiments, the fourth layer has a thickness of at least 200nm. In some embodiments, the fourth layer has a thickness of at least300 nm. In some embodiments, the fourth layer has a thickness of atleast 400 nm. In some embodiments, the fourth layer has a thickness ofat least 500 nm. In some embodiments, the fourth layer has a thicknessof at least 1 μm. In some embodiments, the fourth layer has a thicknessof about 200 nm to about 10 μm, preferably about 500 nm to about 5 μm.In some embodiments, the fourth layer has a thickness of 200 nm to 10μm, preferably 500 nm to 5 μm. In some embodiments, the fourth layer hasa thickness of no more than μm. In some embodiments, the second layerhas a thickness of no more than 5 μm.

A coating according to an embodiment of the present invention having afirst layer, second layer, third layer, and fourth layer as describedherein preferably has a total thickness of about 500 nm to about 10 μm,and more preferably of about 2 μm to about 5 μm. In variations of thisembodiment, the coating has a total thickness of no more than 10 μm,preferably no more than 5 μm.

In further embodiments, a coating according to the present invention hasa mean roughness R_(a) of less than 50 nm, preferably less than 25 nm.In some embodiments, the maximum roughness R_(t) of the coating is lessthan 200 nm, preferably less than 150 nm. The values for roughness(e.g., R_(a) and R_(t)) as mentioned herein are obtained by measurementas an average of four 100 μm traces taken at the sample surface with adiamond stylus profilometer. In some embodiments, the coating of thepresent invention is preferably deposited on a clean, polished substratesurface having a mean roughness less than 50 nm and a maximum roughnessless than 200 nm.

In some particular embodiments, a coating of the present invention mayinclude one or more holes. In one such embodiment, one or more holespass through the entire thickness of the coating In some embodiments,the one or more holes extend only partially through the entire thicknessof the coating. In some embodiments, one or more holes are formed bysubstrate inhomogeneity. In some embodiments, one or more holes areformed by the presence of an impurity (e.g., dust) during the formationof the coating. In some embodiments, a coating includes one or moreholes, each hole having a maximum width of about 10 μm. In otherembodiments, each hole has a maximum width of about 4 μm. In someembodiments, a coating includes one or more substantially circular holeshaving a diameter d of no more than 10 μm, preferably no more than 4 μm.In some embodiments, a coating of the present invention has no holes.

Coatings according to embodiments of the invention may provide highresistance towards corrosion-assisted delamination mechanisms such thata coating integrity of at least 20 years, preferably at least 30 years,in vivo can be expected from the coatings. Crack growth speed along theinterfaces of a coating according to some embodiments is lower than0.011 μm per day in simulated body fluid (phophate buffered saline, calfserum) and in vivo. The measured DLC-on-DLC wear with a coating in someembodiments is as low as 0.005 mm³/Mio Cycles.

One embodiment of the present invention also includes methods forproducing a coating on a substrate, e.g., a CoCrMo substrate. Exemplarymethods of the present invention may be used to produce the coatingsdescribed herein. In one embodiment, a method for producing a DLCcoating on a substrate includes depositing an adhesion-promotinginterlayer onto the substrate and depositing a DLC layer onto theadhesion-promoting interlayer.

In some embodiments, depositing an adhesion-promoting interlayerincludes depositing Ta onto the substrate, for example, via sputtering.In some embodiments, a layer of about 10 nm to about 1 μm of Ta isdeposited onto the substrate. In some embodiments, depositing Ta onto aCoCrMo substrate results in a first layer including a Ta(CoCrMo) alloy,e.g., Ta(CoCrMo)_(0.5-2.0), the substrate surface. In some embodiments,depositing Ta onto the CoCrMo substrate further results in a secondlayer including Ta, e.g., alpha-tantalum. In some embodiments,subsequent depositing of a DLC layer onto the adhesion-promotinginterlayer results in the formation of a third layer including Tacarbide and a fourth layer including DLC. In some embodiments, the DLClayer is deposited using a vapor deposition process, for example, plasmaassisted chemical vapor deposition (PACVD). In some embodiments,depositing Ta and depositing DLC are preferably performed under vacuum(e.g., at a pressure of about 5-10⁻⁵ Pa or less).

In some embodiments, the substrate may be cleaned prior to thedeposition of the adhesion-promoting interlayer, for example, to removeany dirt or foreign substances that may interfere with the depositionsteps. In some embodiments, cleaning the substrate optionally includesprecleaning the substrate using one or more chemical solvents (e.g.,acetone and/or ethanol). In further embodiments, the substrate iscleaned via ion bombardment (e.g., Ar⁺ bombardment) to remove a thin(e.g., <1 μm) layer of material from the substrate surface. In preferredembodiments, cleaning the substrate includes removal of oxidic surfacelayers from the substrate (e.g., by sputter cleaning). In someembodiments, removal of oxidic surface layers from the substrateproduces a reactive surface on the substrate.

In some exemplary embodiments, once the substrate (e.g. a CoCrMosubstrate) is treed of oxidic surface layers, the sputtering of tantalumprovides neutral tantalum atoms on the substrate surface. These neutraltantalum atoms form intermetallic phases with the substrate surfaceproducing a first layer featuring interdiffusion and atomic mixing ofthe tantalum and the substrate material. With a CoCrMo substrateaccording to certain embodiments, this results in the alloying of thetantalum and the CoCrMo substrate material, producing a first layer ofTa(CoCrMo), e.g., Ta(CoCrMo)_(0.5-2.0). As additional tantalum issputtered, a second layer establishes on the first layer once the mixingand interdiffusion range of the tantalum into the substrate surface isexceeded. In some embodiments, the interdiffusion range is equal to thethickness of the first layer. The second layer includes primarilytantalum and, in some embodiments, possible minor contaminations in thevacuum chamber such as oxygen. A third layer is formed according tofurther embodiments when the deposition of tantalum is switched toplasma assisted chemical vapor deposition (PACVD) of acetylene, whichleads to impingement of C_(x)H_(y) species onto the surface of thesecond layer and penetration according to the ballistic energy of theC_(x)H_(y) species. The implanted C_(x)H_(y) species form a carbidelayer with the tantalum surface of the second layer (e.g., a Ta carbidelayer). Once the ballistic range of the C_(x)H_(y) species (e.g., thethickness of the third layer and interdiffusion) is exceeded, a fourthlayer of DLC grows via a “subplantation” process as, for example,described in Lifshitz et al., “Subplantation model for film growth fromhyperthermal species,” Physical Review B, Vol. 41, No. 15, 15 May 1990,which is incorporated herein by reference in its entirety.

An example method for coating a substrate according to one embodiment ofthe present invention includes one or more of the following:

-   -   1. Precleaning of the substrate for about five minutes, for        example, by immersion into a 1:1 mixture of acetone and ethanol        in an ultrasonic cleaner.    -   2. Inserting the substrate into a vacuum system chamber        featuring an RF-powered sample holder and a magnetron sputtering        apparatus and establishing a base pressure, for example, of less        than 5·10⁻⁵ Pa.    -   3. Cleaning of the substrate by argon ion (Ar⁺) bombardment, for        example, by igniting an Ar plasma by application of a 13.56 MHz        radiofrequency voltage to the sample holder with respect to the        grounded chamber walls. Through automatic adjustment of hie RF        power, an RF bias of about −600 V between these points may be        established at an Ar pressure of about 2 Pa. In some        embodiments, this cleaning step results in removal of approx.        140 mm of material from the substrate surface by sputtering and        may take about 30 min.    -   4. Cleaning of the Ta sputtering target by burn-in, for example,        the Ta target is sputtered at high power behind an appropriate        cover (shutter) while the substrate is further kept from        oxidizing by argon bombardment. In some embodiments, the working        pressure is about 2·10⁻¹ Pa Argon and the duration of this step        is from about 2 to about 5 min. The DC magnetron operating        parameters according to some embodiments are U=−435 V, (P=200 W,        I=450 mA). The RE-bias used in some embodiments for substrate        ion bombardment is about −300 V.    -   5. Depositing a Ta adhesion promoting interlayer (e.g., of        thickness 100 nm) onto the substrate. To facilitate this, in        some embodiments the shutter is opened while simultaneously        ceasing the ion bombardment onto the substrate surface. The DC        sputtering parameters may be the same as the previous step, and        the RF bias on substrate holder is 0 V. An example deposition        rate of Ta is about 20 nm/min according to some embodiments,        which therefore results in a Ta thickness of about 100 nm after        about five minutes.    -   6. Deactivating of the DC magnetron while simultaneously        initiating DLC growth. In some embodiments, growth of DLC can be        performed by a PV) or CVD process, preferably plasma assisted        chemical vapor deposition (PACVD) using acetylene gas and a bias        voltage applied to the substrate holder. Example working        pressures may be about 2.5 Pa C₂H₂ with an RF bias on the        substrate holder of about −600 V. In some embodiments the        deposition rate of DLC is about 30 nm/min. The resulting DLC        layer thickness, in some embodiments, is about 2 μm to about 4        μm after a duration of about 60 to about 120 min.    -   7. Allowing the coated substrate to cool in vacuum and removing        the coated substrate from the chamber.

In some embodiments, the oxygen (contaminant) flow into the processchamber can be determined from mass spectrometry measurements providedthat the Ar flow into the chamber is known. In the example method above,the oxygen flow is purposefully adjusted before process start via them/e (O₂ ⁺(32)/Ar⁺(40)) ratio at a known Ar flow using an oxygen leakvalve. The resulting chemical composition of the adhesion promotinginterlayer (second layer) can be obtained from characterization methodslike x-ray photoelectron spectroscopy (XPS) and is also characteristicfor the oxygen content in layers (third layer) and (first layer). Thischemical information can in turn be linked to layer performance inappropriate tests (spine simulators, delamination tests). This permitsdefining tolerance limits for oxygen and to implement an on-linemonitoring system for interlayer stability for a given deposition systemand a given process setting.

The substrate on which the coatings of the present invention may bedeposited can be flat or curved. For example, the substrate may beparticularly shaped for ball-on-socket articulation or for point contactarticulations. Due to its elevated hardness (e.g., about 10 GPa to about80 GPa as measured by nanoindentation), the multilayer coating accordingto some embodiments of the present invention may withstand highmechanical stress encountered with point contact conditions (e.g., 4 GPacompressive stress). The DLC-coated part can be favorably used incombination with a counterpart substrate bearing the same coatingaccording to embodiments of the invention.

FIG. 1 shows an example uncoated (left) and a coated (right) CoCrMospinal disk implant provided with a coating according to an embodimentof the invention resistant to corrosion-assisted delamination. Thecoating system for this sample included a 3 nm, thick Ta(CoCrMo) layer,a 100 nm thick Ta layer, a 5 nm thick Ta-carbide layer and a 4 μm thickDLC layer. The oxygen contamination in the layer system was verified tobe below 3 atomic % inside the adhesion promoting layer system (asmeasured in the Ta layer) by monitoring of the chamber gas compositionduring deposition and related device calibrations. The samples shown inFIG. 1 withstood more than 70 million load cycles in a spine simulatorsetup. Tests in a spinal wear simulator setup show that the wear of suchcoated implants is significantly reduced compared to uncoatedmetal-on-metal tribopairs (FIG. 2).

The accumulated wear volume shown in FIG. 2 was calculated fromgravimetric measurements after a cleaning process as specified in ISO14242-2 (densities DLC 2.8 g/cm³; CoCrMo: 8.29 g/cm³). The metal wearobserved was caused by roughening of the initially smooth metal surface.Furthermore, nanoscale analysis showed that plastic impressions of thehard coating (“eggshell effect”) do not cause cracks to propagate alongthe coating-substrate interface, which could lead to delamination andimplant failure.

FIGS. 3A and 3B show an example defect caused by a hard particle insidethe tribocontact (“eggshell effect”). The coating shown in FIGS. 3A and3B has an oxygen content of less than 0.3 atomic %. As shown in FIG. 3B,this system has been found to be tolerant towards isolated defects;small defects caused, for example by scratches penetrating into thesubstrate, will not expand via one of the described failure mechanismsand coalesce into macroscopic defects, leading to implant failure, suchas observed on prior art implants. Moreover, long-time monitoring ofRockwell indents, holes punctured into the surface by means of aRockwell tip having a conical diamond tip with an angle of about 120degrees at a defined load (example here: 1500 N), while immersing theimplants in saline solution results in no observed tendency ofstress-corrosion cracking.

Layers with an oxygen content exceeding the limits defined according toembodiments of the invention may propagate the crack along the thirdlayer. For example, as shown in FIG. 4, a layer system in one embodimenthaving an oxygen content of 3.5 atomic % may propagate a crack along thethird layer, leading to possible delamination and implant failure afterseveral thousand loading cycles.

As shown in FIG. 5 X-ray diffraction measurements (XRD) on oxygencontaminated. Ta interlayers (Bragg-Brentano geometry) reveal that thealpha-phase tantalum (“α-Ta (110)”) peak disappears at rising oxygencontamination levels. The alpha-phase peak is caused by constructiveinterference of the x-rays on planes of crystallites featuring therespective lattice spacing, as shown here, the spacing of alpha-tantalumin 110 lattice direction. FIG. 5 shows the alpha-phase peak disappearswith the addition of oxygen, indicating a structural change of theadhesion promoting interlayer; the alpha phase disappearance is linkedto a deterioration of the interlayer properties caused by increasingoxygen contamination.

The tantalum interlayer structure is thus assumed to change completely.The phase change occurs simultaneous to mechanical failure of the testsamples. It is thus assumed that the phase change leads to loss ofstability of the Ta/DLC interface as observed with Focused Ion Beam(FIB), a method using a jet of accelerated ions to cut through a sample,delivering a highly polished cross-cut particularly suited for analysiswith a high resolution SEM. This may open another route to diagnose thestability of the Ta interlayer.

Referring to FIG. 5, the intensities and widths of the main peaksindicate that the tantalum layer contains beta-phase tantalum,nano-crystalline alpha-phase tantalum and amorphous tantalum. The 2theta (or 2-θ) peak of alpha-phase tantalum is found at 38° and the 2-θpeak of beta-phase tantalum is found at 34° as one of skill in the artwill understand. The following peak intensities andfull-width-half-maximum values can be established from FIG. 5 for thethree samples (no oxygen, 4 at. % oxygen, 5 at. % oxygen)

TABLE 1 Peak Intensities And Full-Width-Half-Maximum Values EstablishedBased On FIG. 5 Beta-phase Beta-phase Alpha-phase Alpha-phase tantalum(002) tantalum (002) tantalum (110) tantalum (110) Sample Intensity[a.u.] FWHM (deg) Intensity [a.u.] FWHM [deg] No oxygen 265151 0.2034855 0.45 4 at. % oxygen 709636 0.10 1738 1.43 5 at. % oxygen 7294710.08 — —

The peak intensities can be compared using the respective structurefactors F_(x) and the plane multiplicity m_(x). The relationship, F_(x)²·mx links the observed intensity to the actual crystal volume involvedin scattering. For alpha-phase tantalum (110), F=14, m=12 giving anintensity factor of 2352. For beta-phase tantalum (002), F=2, m=2 givingan intensity factor of 8. Therefore, at comparable layer thickness, thetotal crystalline volume in the samples can be calculated from the wellknown equation of Volume=Intensity (beta,(002))/8+intensity(alpha,(110))/2352.

TABLE 2 Comparison of The peak intensities of Table 1 Using TheRespective Structure Factors F_(x) And The Plane Multiplicity m_(x)Total Beta-phase Alpha-phase Amorphous crystalline tantalum (002)tantalum (110) tantalum Sample volume [a.u.] (estimated, wt. %)(estimated, wt. %) (estimated, wt. %) No oxygen 33159 36.3 0.016 63.7 4at. % oxygen 88705 97.3 8.1 · 10⁻⁴ 2.7 5 at. % oxygen 91184 100 0 0

Because the layer volume was comparable at all oxygen levels, anon-crystalline. i.e. amorphous, component is the source of theundetected amount of the crystalline volume. Therefore, the oxygen-freesample contains a high amount of amorphous tantalum. This is furthercorroborated by calculating the crystallite size from the peak FWHMusing the well-known Scherrer Formula.

TABLE 3 Caculated Crystallite Size From The Peak FWHM (Using ScherrerFormula) Beta-phase tantalum (002) Alpha-phase tantalum (110) Samplecrystallite size [nm] crystallite size [nm] No oxygen 43.3 19.5 4 at. %oxygen 86.7 6.1 5 at. % oxygen 108.3 —

This data demonstrates that the oxygen-free layer contains smallercrystallites, evidence of a, nanocrystalline and amorphous structure forthe tantalum layer. As amorphous materials possess high elasticproperties, amorphous tantalum is beneficial as adhesive interlayer asclaimed in this disclosure.

The coatings according to the above examples can be adapted to hipjoints and other medical devices and implants without loss offunctionality. Other example medical devices for which a coatingaccording to embodiments of the present invention may be used includeKirschner wires, intramedullary nails, bone screws, dental implants. Insome embodiments, a coating according to the present invention may beuseful for other devices subject to wear, including non-medical devices,such as for example, machine parts, gears, and tools. In someembodiments, a coating according to the present invention may beparticularly useful for devices subject to wear at temperatures below300° C.

It should be understood that various changes, substitutions, andalterations can be made herein without departing from the spirit andscope of the invention as defined by the appended claims. Moreover, thescope of the present application is not intended to be limited to theparticular embodiments of the process, machine, manufacture, andcomposition of matter, means, methods and steps described in thespecification. As one of ordinary skill in the art will readilyappreciate from the disclosure herein, processes, machines, manufacture,composition of matter, means, methods, or steps, presently existing orlater to be developed that perform substantially the same function orachieve substantially the same result as the corresponding embodimentsdescribed herein may be utilized according to the present invention.

1. A coating for a CoCrMo substrate comprising: a first layer comprisingTa(CoCrMo)_(0.5-2.0); a second layer comprising tantalum; a third layercomprising tantalum carbide; and a fourth layer comprising diamond-likecarbon (DLC).
 2. The coating according to claim 1, wherein the tantalumof the second layer comprises alpha-tantalum.
 3. The coating accordingto claim 1, wherein the second layer is essentially free ofbeta-tantalum.
 4. The coating according to claim 1, wherein the firstlayer has a thickness of about 1 nm to about 5 nm.
 5. The coatingaccording to claim 1, wherein the second layer has a thickness of atleast 20 nm.
 6. The coating according to claim 1, wherein the thirdlayer has a thickness of at least 0.5 nm.
 7. The coating according toclaim 1, wherein the fourth layer has a thickness of at least 200 nm. 8.The coating according to claim 1, wherein the fourth layer has ahydrogen content of less than 35 atomic %.
 9. The coating according toclaim 1, wherein the first layer, the second layer, and the third layereach has an oxygen content lower than 5 atomic %.
 10. The coatingaccording to claim 1, wherein the coating has a mean roughness R_(a)below 50 nm.
 11. The coating according to claim 1, wherein the coatinghas a maximum roughness R, below 200 nm.
 12. The coating according toclaim 1, wherein total thickness of all four layers is in the range ofabout 0.5 μm to about 10 μm.
 13. The coating according to claim 1,wherein the second layer is doped with tungsten, niobium or titanium.14. A device comprising a substrate with a coating according to claim 1.15. The device according to claim 14, wherein said coating is penetratedby a hole reaching the substrate.
 16. The device according to claim 15,wherein said hole has a diameter d≦10 micrometers.
 17. The deviceaccording to claim 14, wherein the device is a joint prosthesis.
 18. Amethod for applying a coating to a CoCrMo substrate comprising thefollowing steps: a) inserting the CoCrMo substrate into a vacuum system;b) cleaning the CoCrMo substrate by Ar⁺ ion bombardment; c) depositing aTa adhesion-promoting interlayer onto the CoCrMo substrate; and d)initiating DLC growth on the Ta adhesion-promoting interlayer.
 19. Themethod according to claim 18, wherein the Ta adhesion-promotinginterlayer is deposited onto the CoCrMo substrate by sputtering.
 20. Themethod according to claim 18, wherein the Ta adhesion-promotinginterlayer has a thickness of about 10 nm to about 1 μm.
 21. The coatingaccording to claim 1, wherein the second layer includes amorphous alphatantalum and nanocrystalline alpha tantalum.
 22. The coating accordingto claim 1, wherein the second layer consists essentially of amorphousalpha tantalum and nanocrystalline alpha tantalum.